CN105542142B - A kind of preparation method of poly- (carbonic ester ether) polyalcohol - Google Patents
A kind of preparation method of poly- (carbonic ester ether) polyalcohol Download PDFInfo
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- CN105542142B CN105542142B CN201610027388.3A CN201610027388A CN105542142B CN 105542142 B CN105542142 B CN 105542142B CN 201610027388 A CN201610027388 A CN 201610027388A CN 105542142 B CN105542142 B CN 105542142B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/42—Chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
Abstract
The invention provides the preparation method of poly- (carbonic ester ether) polyalcohol of one kind, comprise the following steps：With rear-earth-doped based on Zn3[Co(CN)6]2Double metal cyanide catalyst and chain-transferring agent in the presence of, expoxy propane and carbon dioxide are carried out into copolyreaction, obtain the first poly- (carbonic ester ether) polyalcohol；Blocked after described first poly- (carbonic ester ether) polyalcohol, oxirane are mixed with expoxy propane, obtained poly- (carbonic ester ether) polyalcohol.During poly- (carbonic ester ether) polyalcohol is prepared, using oxirane and expoxy propane as end-capping reagent, proportion of primary OH groups is higher in can making poly- (carbonic ester ether) polyalcohol for the application.Test result indicate that, the proportion of primary OH groups of poly- (carbonic ester ether) polyalcohol prepared by the present invention is 50~90mol%.
Description
Technical field
The present invention relates to polymer polyatomic alcohol technical field, more particularly to a kind of preparation of poly(carbonate-ether) polyol
Method.
Background technology
Poly(carbonate-ether) polyol refers to carbonate unit and ether unit containing repetition, strand in molecular backbone
End be the one of hydroxyl and birds of the same feather flock together compound.Poly(carbonate-ether) polyol is close with PEPA and PPG, its
One of primary raw material of polyurethane industrial, be widely used in manufacture automotive upholstery, train steamer gadget, medicine equipment, household electrical appliances,
The fields such as furniture, woven lining, coating, footwear, leather and slurry.The polyurethane phase synthesized with PEPA and PPG
Than poly- (carbonic ester-ether) type polyurethane prepared by poly(carbonate-ether) polyol has more excellent heat resistance, water-fast
Property, antibiotic property, oxidative resistance and mechanical performance, and some products also have more preferable biological degradability.Meanwhile, poly- (carbonic acid
Ester-ether) polyalcohol can be by carbon dioxide and epoxides copolymerization, therefore, it is possible to " carbon dioxide in environment is become into useless
It is treasured ".
Oxirane synthesizes for polyethers earliest, and end group is entirely primary hydroxyl；Expoxy propane is used now using more convenient
More commonly.Application publication number discloses a kind of preparation side of poly(carbonate-ether) polyol for the Chinese patent of CN102617844
Method, it is utilized, and rear-earth-doped double metal cyanide (DMC) is catalyzed carbon dioxide and propylene oxide copolymer prepares low-molecular-weight and gathers
(carbonic ester-ether) polyalcohol, but it is catalyzed the copolymer of carbon dioxide and expoxy propane, and end group proportion of primary OH groups is relatively low, is less than
20%.
In the presence of dmc catalyst, the poly(carbonate-ether) polyol of generation is mainly produced for carbon dioxide and expoxy propane
Raw secondary hydroxyl.Because the reactivity of primary hydroxyl is about 3 times of secondary hydroxyl, highly beneficial is synthesized to polyurethane, therefore primary hydroxyl high
Poly(carbonate-ether) polyol is always the target of pursuit.Researcher using ethylene oxide-capped it is contemplated that improve primary hydroxyl
Content, but the poly(carbonate-ether) polyol being made of bimetallic catalyst series (DMC), although have narrow molecular weight distribution,
The molecular weight height low advantage of adjustable, degree of unsaturation, but DMC catalysis activities are very high, when ethyleneoxide addition reaction is carried out, make
The chain growth speed for obtaining oxirane is faster than chain tra nsfer speed, makes the polyoxyethylene having in poly(carbonate-ether) polyol finished product
Alkene side chain is very long, and oxirane chain link is few even without so as to cause the length inequality of strand, oxirane on some segments
Skewness, the proportion of primary OH groups of poly(carbonate-ether) polyol is low.PPG is usually using the relatively low KOH of activity
Dmc catalyst is substituted as catalyst, carries out ethyleneoxide addition reaction to prepare the PPG of high proportion of primary OH groups.
But poly(carbonate-ether) polyol can degrade rapidly in the presence of KOH, thus this method be not suitable for it is poly- (carbonic ester-
Ether) polyalcohol end-blocking.
Due to poly(carbonate-ether) polyol proportion of primary OH groups number have on reactivity directly influence, because
The raising of this poly(carbonate-ether) polyol proportion of primary OH groups has turned into the problem that many researchers are concerned about, is always the research
Emphasis and difficult point.
The content of the invention
Present invention solves the technical problem that being to provide a kind of preparation method of poly(carbonate-ether) polyol, the application
The proportion of primary OH groups of the poly(carbonate-ether) polyol of preparation is higher.
In view of this, this application provides a kind of preparation method of poly(carbonate-ether) polyol, comprise the following steps：
With rear-earth-doped based on Zn3[Co(CN)6]2Double metal cyanide catalyst and chain-transferring agent effect
Under, expoxy propane and carbon dioxide are carried out into copolyreaction, obtain the first poly(carbonate-ether) polyol；
Blocked after first poly(carbonate-ether) polyol, oxirane are mixed with expoxy propane, gathered
(carbonic ester-ether) polyalcohol.
Preferably, in the step of obtaining poly(carbonate-ether) polyol, the oxirane and the expoxy propane
Mol ratio is (0.5~10)：1.
Preferably, in the step of obtaining poly(carbonate-ether) polyol, the oxirane and the expoxy propane
Mol ratio is (1~9)：1.
Preferably, the gross mass of oxirane described in the step of obtaining poly(carbonate-ether) polyol and expoxy propane
It is (0.1~1) with the ratio for obtaining the quality of expoxy propane described in the first poly(carbonate-ether) polyol：1.
Preferably, during the first poly(carbonate-ether) polyol is obtained, the catalyst and the expoxy propane
Mass ratio be 1：(1000~200000).
Preferably, during the first poly(carbonate-ether) polyol is obtained, the expoxy propane and the chain tra nsfer
The mass ratio of agent is (2~25)：1.
Preferably, the chain-transferring agent is selected from small molecular alcohol, the oligomer of hydroxyl, aliphatic carboxylic acid, alicyclic carboxylic acid
With one or more in aromatic carboxylic acid.
Preferably, the small molecular alcohol is selected from ethylene glycol, 1,2-PD, 1,3-PD, BDO, 1,2- fourth
Glycol, 1,3-BDO, 1,5-PD, 1,5- hexylene glycols, 1,6- hexylene glycols, ethohexadiol, decanediol, 1,3- rings pentanediol,
1,2- cyclohexanediol, 1,3- cyclohexanediols, Isosorbide-5-Nitrae-cyclohexanediol, 1,2-CHDM, diethylene glycol, triethylene glycol, four
Ethylene glycol, DPG, tripropylene glycol, polypropylene glycol, trimethylolethane, trimethylolpropane, glycerine, 1,2,4- fourths three
One or more in alcohol, polyester triol and pentaerythrite；It is poly- less than 2000 that the oligomer of the hydroxyl is selected from molecular weight
One kind or many in the PolyTHF dihydroxylic alcohols of the polypropylene glycol of ethylene glycol, molecular weight less than 2000 and molecular weight less than 2000
Kind.
Preferably, the aliphatic carboxylic acid is selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, pungent two
Acid, azelaic acid, decanedioic acid, dodecanedioic acid, 1,3- acetone dicarboxylic acids, tartaric acid, malic acid, citric acid, acetylenedicarboxylic acid and
One or more in trans-aconitic acid；The alicyclic carboxylic acid is selected from 1,2- cyclohexyl dicarboxylic acids, 1,3- cyclohexyl dicarboxylic acids and 1,
One or more in 4- cyclohexyl dicarboxylic acids；The aromatic carboxylic acid is selected from phthalic acid, M-phthalic acid, terephthaldehyde
Acid, phthalic acid, a phenylenediacetic Acid and to phenylenediacetic Acid in one or more.
Preferably, the temperature of the copolyreaction is 5~120 DEG C, and the pressure of the copolyreaction is 1~12MPa, described
The time of copolyreaction is 1~48h.
This application provides a kind of preparation method of poly(carbonate-ether) polyol, it is first by expoxy propane and dioxy
Change carbon with rear-earth-doped based on Zn3[Co(CN)6]2Double metal cyanide catalysis and chain-transferring agent in the presence of occur
Copolyreaction, has obtained the first poly(carbonate-ether) polyol, then adds oxirane and is blocked with expoxy propane,
Obtain poly(carbonate-ether) polyol.The application, as end-capping reagent, can make ring using the mixture of oxirane and expoxy propane
Oxidative ethane is distributed evenly in the two ends of polyalcohol chain, and obtains the poly(carbonate-ether) polyol of primary hydroxyl high.Experimental result
Show, the proportion of primary OH groups of poly- (carbonic ester-ether) polyalcohol prepared by the application is 50~90mol%.
Brief description of the drawings
Fig. 1 is the GPC curves of poly(carbonate-ether) polyol prepared by the embodiment of the present invention 1；
Fig. 2 is poly(carbonate-ether) polyol prepared by the embodiment of the present invention 11H-NMR collection of illustrative plates；
Fig. 3 is the TFAA ester of poly(carbonate-ether) polyol prepared by the embodiment of the present invention 119F-NMR schemes
Spectrum.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, but
It should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
The embodiment of the invention discloses a kind of preparation method of poly(carbonate-ether) polyol, comprise the following steps：
With rear-earth-doped based on Zn3[Co(CN)6]2Double metal cyanide catalyst and chain-transferring agent effect
Under, expoxy propane and carbon dioxide are carried out into copolyreaction, obtain the first poly(carbonate-ether) polyol；
Blocked after first poly(carbonate-ether) polyol, oxirane are mixed with expoxy propane, gathered
(carbonic ester-ether) polyalcohol.
The application by expoxy propane, carbon dioxide with rear-earth-doped based on Zn3[Co(CN)6]2Double metal cyanide
(DMC) in the presence of catalyst and chain-transferring agent, be copolymerized, obtain poly(carbonate-ether) polyol, then thereto plus
Entering expoxy propane and oxirane carries out addition polymerization end-blocking, has obtained poly(carbonate-ether) polyol.The application with expoxy propane with
Oxirane can make the proportion of primary OH groups of poly(carbonate-ether) polyol high as end-capping reagent.
During poly(carbonate-ether) polyol is prepared, the application is first by expoxy propane and carbon dioxide in DMC
Copolyreaction is carried out in the presence of catalyst and chain-transferring agent, poly(carbonate-ether) polyol is obtained.In the process, chain turns
The effect for moving agent is to control molecular weight and terminal hydroxy group quantity；Herein described chain-transferring agent is preferably small molecular alcohol, hydroxyl
Oligomer, aliphatic carboxylic acid, alicyclic carboxylic acid and aromatic carboxylic acid in one or more.
The small molecular alcohol be selected from ethylene glycol, 1,2-PD, 1,3-PD, BDO, 1,2- butanediol, 1,
3- butanediols, 1,5-PD, 1,5- hexylene glycols, 1,6- hexylene glycols, ethohexadiol, decanediol, 1,3- rings pentanediol, 1,2- hexamethylenes
Glycol, 1,3- cyclohexanediols, Isosorbide-5-Nitrae-cyclohexanediol, 1,2-CHDM, diethylene glycol, triethylene glycol, TEG, two
Propane diols, tripropylene glycol, polypropylene glycol, trimethylolethane, trimethylolpropane, glycerine, BT, polyester triol
With one or more in pentaerythrite.
The oligomer of the hydroxyl is selected from poly- the third two of polyethylene glycol of the molecular weight less than 2000, molecular weight less than 2000
One or more in the PolyTHF dihydroxylic alcohols of alcohol and molecular weight less than 2000.
The aliphatic carboxylic acid is selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, nonyl two
Acid, decanedioic acid, dodecanedioic acid, 1,3- acetone dicarboxylic acids, tartaric acid, malic acid, citric acid, acetylenedicarboxylic acid and the trans rhizome of Chinese monkshood
One or more in acid.
The alicyclic carboxylic acid is selected from 1,2- cyclohexyl dicarboxylic acids, 1,3- cyclohexyl dicarboxylic acids and Isosorbide-5-Nitrae-cyclohexyl dicarboxylic acid
Plant or various；The aromatic carboxylic acid is selected from phthalic acid, M-phthalic acid, terephthalic acid (TPA), phthalic acid, isophthalic two
Acetic acid and to phenylenediacetic Acid in one or more.
Preferably, in embodiment, the chain-transferring agent be preferably decanedioic acid, PPG-300, trans-aconitic acid,
Oxalic acid, phthalic acid or ethylene glycol.The application has no particular limits to the source of the chain-transferring agent, using commercially available prod
.
The application has no particular limits to the source of the dmc catalyst, preferably, can be according to Publication No.
Method disclosed in the Chinese patent of CN102617844 is prepared, and detailed process is：
The tert-butyl alcohol, water, zinc salt compound and rare earth salt compound are mixed, mixing salt solution is obtained；
To adding K in the aggregate sample solution3[Co(CN)6] solution, being separated after stirring, washing is dried, and is obtained rare earth and is mixed
It is miscellaneous based on Zn3[Co(CN)6]2Double metal cyanide.
During the poly(carbonate-ether) polyol of above-mentioned preparation first, the catalyst and the expoxy propane
Mass ratio is preferably 1：(1000~200000), more preferably 1:(2000~10000).The expoxy propane and the chain tra nsfer
The mass ratio of agent is preferably (2~25)：1, more preferably (4~10)：1.In the poly(carbonate-ether) polyol of above-mentioned preparation first
During, reaction condition of the carbon dioxide with the expoxy propane in copolyreaction can influence it is first poly- (carbonic ester-
Ether) performance such as carbonate content in polyalcohol.The temperature of the copolyreaction is preferably 5~120 DEG C, described in embodiment
The temperature of copolyreaction is more preferably 40~100 DEG C；The pressure of the copolyreaction is preferably 1~12MPa, in embodiment,
The pressure of the copolyreaction is more preferably 2~7MPa；The time of the copolyreaction is preferably 1~48h, in embodiment,
The time of the copolyreaction is more preferably 2~24h.
The application is blocked after mixing first poly(carbonate-ether) polyol, oxirane and expoxy propane,
Obtain poly(carbonate-ether) polyol.During this, the mol ratio of oxirane and expoxy propane can influence it is poly- (carbonic ester-
Ether) polyalcohol proportion of primary OH groups；The oxirane is preferably (0.5~10) with the mol ratio of the expoxy propane：1, more
Preferably (1~9)：1.The amount of primary hydroxyl is with ethylene oxide content in poly(carbonate-ether) polyol prepared by the application
Increase and increase, if but all oxirane, the content of primary hydroxyl can reduce.Oxirane and ring during end-blocking
The gross mass of Ethylene Oxide is preferably (0.1~1) with the mass ratio of copolyreaction oxypropylene：1, more preferably (0.2~
0.5)：1.Oxirane depends primarily on the amount of oxirane with the gross mass of expoxy propane；Excessive introducing oxirane meeting
The transparency of product is caused to die down, cost increase, carbonate unit content declines, the storing dangerous property increase of raw material, therefore it is logical
Few addition oxirane is to try in the case of often；But add very few the also resulting in of oxirane to react incomplete, primary hydroxyl contains
Amount is low.Therefore oxirane needs molecular weight, the carbonic ether unit content according to the product for obtaining with the gross mass of expoxy propane
And proportion of primary OH groups is specifically adjusted.
In order that prepare the raw material reaction of poly(carbonate-ether) polyol fully, it is preferably, herein described poly-
The preparation process of (carbonic ester-ether) polyalcohol is specially：
Measuring cup is evacuated at 80 DEG C and fills CO2Treatment 2h (inflation 6 times), and it is cooled to room temperature；In CO2(99.99%)
To dmc catalyst and chain-transferring agent is added in measuring cup under protection, mixture is obtained；
By 500ml reactors at 80 DEG C, CO is filled through evacuating2Treatment 2h (inflation 6 times), and room temperature is cooled to, to described
The mixture and propylene oxide monomer are added in reactor, is stirred with the rotating speed of 500rpm, adjusted by pressure carbon dioxide
To carbon dioxide is passed through in kettle, reactor is inserted carries out polymerisation to device in constant temperature bath；
After question response terminates, unreacted carbon dioxide is discharged, the mixture for adding oxirane and expoxy propane enters
Row addition polymerization is blocked, and obtains poly(carbonate-ether) polyol.
Additionally, said process further preferably includes：To adding solvent in the reactor；For being in polymerization process
No addition solvent, there is no particular restriction for the present invention.
The poly(carbonate-ether) polyol is mixed with expoxy propane, dilution is obtained；Filter the dilution removal
Dmc catalyst, distills, dries.The process is specially：
Room temperature will be cooled to for the cold bath that the reactor temperature of polymerisation is 12~15 DEG C, slow discharge is not anti-
The residual carbon dioxide answered, and to addition expoxy propane in reactor until poly(carbonate-ether) polyol is diluted to and is beneficial to
By glass sand core funnel, dilution is obtained；Catalyst is removed with glass sand core funnel filtered dilutions, filtrate is evaporated off epoxy third
Alkane, residue is dried to constant weight in 40 DEG C of vacuum drying chambers, so as to obtain primary hydroxyl poly(carbonate-ether) polyol high.
Poly(carbonate-ether) polyol prepared by the application can be used to prepare polyurethane foam, polyurethane elastomer and gather
Urethane adhesive etc..
In the presence of dmc catalyst and chain-transferring agent, be copolymerized for expoxy propane, carbon dioxide by the present invention,
The first poly(carbonate-ether) polyol is obtained, the mixture for being subsequently adding oxirane and expoxy propane carries out addition polymerization end-blocking, obtains
To poly(carbonate-ether) polyol.The present invention prepares poly(carbonate-ether) polyol using " one pot reaction ", and in
Between process the polymer containing dmc catalyst, then in the same reactor and under same dmc catalyst, as end-capping reagent
Oxirane and propylene oxide mixture carry out addition polymerization, be capable of achieving a series of with different carbonic esters/ehter bond ratio and primary hydroxyl
The synthesis of the poly(carbonate-ether) polyol of base ratio, and have certain stability, range of application under heating, stirring condition
It is wider.
Poly(carbonate-ether) polyol prepared by the application has the advantage of PPG and PEPA, molecule concurrently
The ratio of carbonic ester section and ether section can be adjusted in chain, and structure can easily be accommodated, and range of application is wider.Additionally, compared to other lifes
Biodegradable material, herein described poly(carbonate-ether) polyol is with CO2It is cheap as raw material, reaction condition temperature
With stability is high, pollutes less, more environmentally friendly in technique.Result of the test shows that poly- (carbonic ester-ether) prepared by the present invention is polynary
The proportion of primary OH groups of alcohol is 50~90mol%, and carbonic ester segment content is still higher, is 30wt%~80wt%, and molecular weight is
1000g/mol~30000g/mol, molecular weight distribution is 1.07~1.40.
For a further understanding of the present invention, with reference to the poly(carbonate-ether) polyol that embodiment is provided the present invention
Preparation method be described in detail, protection scope of the present invention is not limited by the following examples.
Embodiment 1
Measuring cup is evacuated at 80 DEG C and fills CO2Gas disposal 2h (inflation 6 times), and it is cooled to room temperature；In CO2The protection of gas
Lower dmc catalyst and 1.15g decanedioic acid chain-transferring agents to addition 10.0mg in measuring cup, obtains mixture；500ml is reacted
Kettle fills CO at 80 DEG C through evacuating2Treatment 2h (inflation 6 times), and be cooled to room temperature, to adding the mixing in the reactor
Thing, is then act through the connection of catalyst measuring cup to 10ml expoxy propane is added in kettle, is stirred with the rotating speed of 500rpm, by two
To carbon dioxide is passed through in kettle, reactor is inserted carries out polymerisation, polymerisation to carbon oxide pressure adjuster in constant temperature bath
Middle pressure carbon dioxide 4.0Mpa, 80 DEG C of the temperature of polymerisation, the time 2h of polymerisation.
After polymerisation terminates, unreacted monomer and carbon dioxide are slowly discharged, and to 5ml moles of addition in reactor
Than being 0.5：1 oxirane and the mixture of expoxy propane, continue to react 2h；After reaction terminates, by for polymerisation
Reactor temperature is that 12~15 DEG C of cold bath is cooled to room temperature, and makes polymer dilute to addition expoxy propane in reactor
Release to beneficial to the degree filtered by G2 glass sand core funnel, catalyst removed using G2 glass sand core funnels filtered dilutions,
Filtrate is evaporated off expoxy propane, and residue is dried to constant weight in 40 DEG C of vacuum drying chambers, so as to obtain the poly- (carbonic acid of primary hydroxyl high
Ester-ether) polyalcohol 17.5g.
Primary hydroxyl poly(carbonate-ether) polyol high manufactured in the present embodiment is analyzed using GPC, as shown in figure 1,
Fig. 1 is the GPC curves of poly(carbonate-ether) polyol manufactured in the present embodiment, from figure 1 it appears that this is poly- (carbonic ester-
Ether) polyalcohol number-average molecular weight be 2900g/mol, molecular weight distribution is 1.20.Fig. 2 is primary hydroxyl high manufactured in the present embodiment
Poly(carbonate-ether) polyol1H-NMR collection of illustrative plates, as a result shows, 50.3% carbon is contained in poly(carbonate-ether) polyol
Acid esters unit.Fig. 3 is the TFAA ester of primary hydroxyl poly(carbonate-ether) polyol high manufactured in the present embodiment19F-NMR
Analysis, as a result shows, the primary hydroxyl containing 52.0mol% in poly(carbonate-ether) polyol manufactured in the present embodiment.
Embodiment 2
Measuring cup is evacuated at 80 DEG C and fills CO2Gas disposal 2h (inflation 6 times), and it is cooled to room temperature；In CO2The protection of gas
Lower dmc catalyst and 1.0g PPG-300 chain-transferring agents to addition 5.0mg in measuring cup, obtains mixture；500ml is reacted
Kettle fills CO at 80 DEG C through evacuating2Treatment 2h (inflation 6 times), and be cooled to room temperature, to adding the mixing in the reactor
Thing, is then act through the connection of catalyst measuring cup to 10ml expoxy propane is added in kettle, is stirred with the rotating speed of 500rpm, by two
To carbon dioxide is passed through in kettle, reactor is inserted carries out polymerisation, polymerisation to carbon oxide pressure adjuster in constant temperature bath
Pressure carbon dioxide be 2.0Mpa, the temperature of polymerisation is 60 DEG C, and the time of polymerisation is 4h.
After polymerisation terminates, unreacted monomer and carbon dioxide are slowly discharged, and to 6ml moles of addition in reactor
Than being 2：1 oxirane and the mixture of expoxy propane, continue to react 4h.Post processing obtains primary hydroxyl high and gathers with embodiment 1
(carbonic ester-ether) polyalcohol 24.3g.
Primary hydroxyl poly(carbonate-ether) polyol high manufactured in the present embodiment is analyzed using GPC, result of the test table
Bright, the equal molecule of number of poly(carbonate-ether) polyol is 6400g/mol, and molecular weight distribution is 1.38；1H-NMR profiling results tables
It is bright, the carbonate unit containing 35.8wt% in poly(carbonate-ether) polyol manufactured in the present embodiment；Poly- (carbonic ester-ether)
The TFAA ester of polyalcohol19F-NMR analysis results show, in poly(carbonate-ether) polyol manufactured in the present embodiment
Primary hydroxyl containing 66.2mol%.
Embodiment 3
Measuring cup is evacuated at 80 DEG C and fills CO2Gas disposal 2h (inflation 6 times), and it is cooled to room temperature；In CO2The protection of gas
Lower dmc catalyst and 1.6g trans-aconitic acid chain-transferring agents to addition 15.0mg in measuring cup, obtains mixture；By 500ml
Reactor fills CO at 80 DEG C through evacuating2Treatment 2h (inflation 6 times), and room temperature is cooled to, it is described to being added in the reactor
Mixture, is then act through the connection of catalyst measuring cup to 10ml expoxy propane is added in kettle, is stirred with the rotating speed of 500rpm, leads to
Pressurized carbon dioxide draught control mechanism is crossed to carbon dioxide is passed through in kettle, reactor is inserted carries out polymerisation in constant temperature bath, be polymerized
The pressure of the carbon dioxide of reaction is 3.0Mpa, and the temperature of polymerisation is 40 DEG C, and the time of polymerisation is 24h.
After polymerisation terminates, unreacted monomer and carbon dioxide are slowly discharged, and to 8ml moles of addition in reactor
Than being 5：1 oxirane and the mixture of expoxy propane, continue to react 4h.Post processing obtains primary hydroxyl high and gathers with embodiment 1
(carbonic ester-ether) polyalcohol 18.1g.
Primary hydroxyl poly(carbonate-ether) polyol high manufactured in the present embodiment is analyzed using GPC, the poly- (carbonic acid
Ester-ether) polyalcohol the equal molecule of number be 3000g/mol, molecular weight distribution is 1.25.1H-NMR profiling results show, this implementation
Carbonate unit containing 77.3wt% in poly(carbonate-ether) polyol prepared by example.The three of poly(carbonate-ether) polyol
Fluoroacetic acid acid anhydride ester19F-NMR analysis results show, the primary hydroxyl containing 74.4mol% in polymer manufactured in the present embodiment.
Embodiment 4
Measuring cup is evacuated at 80 DEG C and fills CO2Gas disposal 2h (inflation 6 times), and it is cooled to room temperature；In CO2The protection of gas
Lower dmc catalyst and 0.68g oxalic acid chain-transferring agents to addition 2.0mg in measuring cup, obtains mixture；By 500ml reactors
At 80 DEG C, CO is filled through evacuating2Treatment 2h (inflation 6 times), and be cooled to room temperature, to adding the mixing in the reactor
Thing, is then act through the connection of catalyst measuring cup to 10ml expoxy propane is added in kettle, is stirred with the rotating speed of 500rpm, by two
To carbon dioxide is passed through in kettle, reactor is inserted carries out polymerisation, polymerisation to carbon oxide pressure adjuster in constant temperature bath
The pressure of carbon dioxide be 5.0Mpa, the temperature of polymerisation is 100 DEG C, and the time of polymerisation is 12h.
After polymerisation terminates, unreacted monomer and carbon dioxide are slowly discharged, and to 4ml moles of addition in reactor
Than being 1：1 oxirane and the mixture of expoxy propane, continue to react 6h.Post processing obtains primary hydroxyl high and gathers with embodiment 1
(carbonic ester-ether) polyalcohol 19.8g.
Primary hydroxyl poly(carbonate-ether) polyol high manufactured in the present embodiment is analyzed using GPC, the poly- (carbonic acid
Ester-ether) polyalcohol the equal molecule of number be 3200g/mol, molecular weight distribution is 1.34.1H-NMR profiling results show, this implementation
Carbonate unit containing 51.1wt% in poly(carbonate-ether) polyol prepared by example.The TFAA ester of polymer19F-NMR analysis results show, the primary hydroxyl containing 58.8mol% in polymer manufactured in the present embodiment.
Embodiment 5
Measuring cup is evacuated at 80 DEG C and fills CO2Gas disposal 2h (inflation 6 times), and it is cooled to room temperature；In CO2The protection of gas
Lower dmc catalyst and 1.8g phthalic acid chain-transferring agents to addition 20.0mg in measuring cup, obtains mixture；By 500ml
Reactor fills CO at 80 DEG C through evacuating2Treatment 2h (inflation 6 times), and room temperature is cooled to, it is described to being added in the reactor
Mixture, is then act through the connection of catalyst measuring cup to 10ml expoxy propane is added in kettle, is stirred with the rotating speed of 500rpm, leads to
Pressurized carbon dioxide draught control mechanism is crossed to carbon dioxide is passed through in kettle, reactor is inserted carries out polymerisation in constant temperature bath, be polymerized
The pressure of the carbon dioxide of reaction is 4.0Mpa, and the temperature of polymerisation is 60 DEG C, and the time of polymerisation is 2h.
After polymerisation terminates, unreacted monomer and carbon dioxide are slowly discharged, and rub to addition 10ml in reactor
You are than being 9：1 oxirane and the mixture of expoxy propane, continue to react 2h.Post processing obtains primary hydroxyl high with embodiment 1
Poly(carbonate-ether) polyol 23.8g.
Primary hydroxyl poly(carbonate-ether) polyol high manufactured in the present embodiment is analyzed using GPC, the polymer
The equal molecule of number is 3500g/mol, and molecular weight distribution is 1.22.1H-NMR profiling results show, poly- (carbonic acid manufactured in the present embodiment
Ester-ether) carbonate unit containing 75.1wt% in polyalcohol.The TFAA ester of poly(carbonate-ether) polyol19F-
NMR analysis results show, the primary hydroxyl containing 83.mol% in polymer manufactured in the present embodiment.
Embodiment 6
Measuring cup is evacuated at 80 DEG C and fills CO2Gas disposal 2h (inflation 6 times), and it is cooled to room temperature；In CO2The protection of gas
Lower dmc catalyst and 0.5g glycol chain transfer agents to addition 4.0mg in measuring cup, obtains mixture；By 500ml reactors
At 80 DEG C, CO is filled through evacuating2Treatment 2h (inflation 6 times), and be cooled to room temperature, to adding the mixing in the reactor
Thing, is then act through the connection of catalyst measuring cup to 10ml expoxy propane is added in kettle, is stirred with the rotating speed of 500rpm, by two
To carbon dioxide is passed through in kettle, reactor is inserted carries out polymerisation, polymerisation to carbon oxide pressure adjuster in constant temperature bath
The pressure of carbon dioxide be 2.0Mpa, the temperature of polymerisation is 80 DEG C, and the time of polymerisation is 6h.
After polymerisation terminates, unreacted monomer and carbon dioxide are slowly discharged, and to 2ml moles of addition in reactor
Than being 4：1 oxirane and the mixture of expoxy propane, continue to react 6h.Post processing obtains primary hydroxyl high and gathers with embodiment 1
(carbonic ester-ether) polyalcohol 18.8g.
Primary hydroxyl poly(carbonate-ether) polyol high manufactured in the present embodiment is analyzed using GPC, the polymer
The equal molecule of number is 2600g/mol, and molecular weight distribution is 1.31.1H-NMR profiling results show, poly- (carbonic acid manufactured in the present embodiment
Ester-ether) carbonate unit containing 30.3wt% in polyalcohol.The TFAA ester of poly(carbonate-ether) polyol19F-
NMR analysis results show, the primary hydroxyl containing 56.8mol% in polymer manufactured in the present embodiment.
Embodiment 7
Measuring cup is evacuated at 80 DEG C and fills CO2Gas disposal 2h (inflation 6 times), and it is cooled to room temperature；In CO2The protection of gas
Lower dmc catalyst and 1.2g trans-aconitic acid chain-transferring agents to addition 25.0mg in measuring cup, obtains mixture；By 500ml
Reactor fills CO at 80 DEG C through evacuating2Treatment 2h (inflation 6 times), and room temperature is cooled to, it is described to being added in the reactor
Mixture, is then act through the connection of catalyst measuring cup to 20ml expoxy propane is added in kettle, is stirred with the rotating speed of 500rpm, leads to
Pressurized carbon dioxide draught control mechanism is crossed to carbon dioxide is passed through in kettle, reactor is inserted carries out polymerisation in constant temperature bath, be polymerized
The pressure of the carbon dioxide of reaction is 5.0Mpa, and the temperature of polymerisation is 60 DEG C, and the time of polymerisation is 8h.
After polymerisation terminates, unreacted monomer and carbon dioxide are slowly discharged, and to 8ml moles of addition in reactor
Than being 10：1 oxirane and the mixture of expoxy propane, continue to react 4h.Post processing obtains primary hydroxyl high with embodiment 1
Poly(carbonate-ether) polyol 27.3g.
Primary hydroxyl poly(carbonate-ether) polyol high manufactured in the present embodiment is analyzed using GPC, the polymer
The equal molecule of number is 3200g/mol, and molecular weight distribution is 1.21.1H-NMR profiling results show, poly- (carbonic acid manufactured in the present embodiment
Ester-ether) carbonate unit containing 78.6wt% in polyalcohol.The TFAA ester of poly(carbonate-ether) polyol19F-
NMR analysis results show, the primary hydroxyl containing 89.2mol% in poly(carbonate-ether) polyol manufactured in the present embodiment.
As seen from the above embodiment, the present invention realizes a series of with different carbonic esters/ehter bond ratio and primary hydroxyl ratio
The synthesis of the poly(carbonate-ether) polyol of example, structure can easily be accommodated, and have certain stability under heating, stirring condition,
Range of application is wider.
The explanation of above example is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that right
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or uses the present invention.
Various modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The scope most wide for causing.
Claims (9)
1. a kind of preparation method of poly(carbonate-ether) polyol, comprises the following steps：
With rear-earth-doped based on Zn3[Co(CN)6]2Double metal cyanide catalyst and chain-transferring agent in the presence of, will
Expoxy propane and carbon dioxide carry out copolyreaction, obtain the first poly(carbonate-ether) polyol；
Blocked after first poly(carbonate-ether) polyol, oxirane are mixed with expoxy propane, obtained poly- (carbon
Acid esters-ether) polyalcohol；The oxirane is (0.5~10) with the mol ratio of the expoxy propane：1.
2. preparation method according to claim 1, it is characterised in that the step of poly(carbonate-ether) polyol is obtained
In, the oxirane is (1~9) with the mol ratio of the expoxy propane：1.
3. preparation method according to claim 1, it is characterised in that the step of poly(carbonate-ether) polyol is obtained
In, the gross mass of the oxirane and expoxy propane with obtain expoxy propane described in the first poly(carbonate-ether) polyol
Quality ratio be (0.1~1)：1.
4. preparation method according to claim 1, it is characterised in that obtaining the first poly(carbonate-ether) polyol
During, the catalyst is 1 with the mass ratio of the expoxy propane：(1000~200000).
5. preparation method according to claim 1, it is characterised in that obtaining the first poly(carbonate-ether) polyol
During, the expoxy propane is (2~25) with the mass ratio of the chain-transferring agent：1.
6. preparation method according to claim 1, it is characterised in that the chain-transferring agent is selected from small molecular alcohol, hydroxyl
Oligomer, aliphatic carboxylic acid, alicyclic carboxylic acid and aromatic carboxylic acid in one or more.
7. preparation method according to claim 6, it is characterised in that the small molecular alcohol is selected from ethylene glycol, 1,2- the third two
Alcohol, 1,3-PD, BDO, 1,2- butanediol, 1,3-BDO, 1,5-PD, 1,5- hexylene glycols, 1,6- oneself two
Alcohol, ethohexadiol, decanediol, 1,3- rings pentanediol, 1,2- cyclohexanediols, 1,3- cyclohexanediols, Isosorbide-5-Nitrae-cyclohexanediol, 1,2- hexamethylenes
Alkane dimethanol, diethylene glycol, triethylene glycol, TEG, DPG, tripropylene glycol, polypropylene glycol, trimethylolethane,
One or more in trimethylolpropane, glycerine, BT, polyester triol and pentaerythrite；The hydroxyl
Oligomer is selected from polyethylene glycol of the molecular weight less than 2000, polypropylene glycol of the molecular weight less than 2000 and molecular weight and is less than 2000
One or more in PolyTHF dihydroxylic alcohols.
8. preparation method according to claim 6, it is characterised in that the aliphatic carboxylic acid is selected from oxalic acid, malonic acid, fourth
Diacid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, dodecanedioic acid, 1,3- acetone dicarboxylic acids, winestone
One or more in acid, malic acid, citric acid, acetylenedicarboxylic acid and trans-aconitic acid；The alicyclic carboxylic acid is selected from 1,2-
One or more in cyclohexyl dicarboxylic acid, 1,3- cyclohexyl dicarboxylic acids and Isosorbide-5-Nitrae-cyclohexyl dicarboxylic acid；The aromatic carboxylic acid is selected from neighbour
Phthalic acid, M-phthalic acid, terephthalic acid (TPA), phthalic acid, a phenylenediacetic Acid and to one kind in phenylenediacetic Acid or many
Kind.
9. preparation method according to claim 1, it is characterised in that the temperature of the copolyreaction is 5~120 DEG C, institute
The pressure of copolyreaction is stated for 1~12MPa, the time of the copolyreaction is 1~48h.
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| CN107868239B (en) * | 2017-11-28 | 2019-11-15 | 中国科学院长春应用化学研究所 | A kind of poly(carbonate-ether) polyol composition and preparation method thereof with high proportion of primary OH groups |
| MA53727A (en) | 2018-09-24 | 2021-12-29 | Saudi Aramco Tech Co | POLYCARBONATE BLOCK COPOLYMERS AND RELATED METHODS |
| CN111471134B (en) * | 2020-05-15 | 2021-09-21 | 中国科学院长春应用化学研究所 | Active hydrogen tolerant catalyst, preparation method thereof and ultra-low molecular weight poly (carbonate-ether) polyol |
| CN112266475B (en) * | 2020-11-05 | 2022-02-22 | 中国科学院长春应用化学研究所 | Carbon dioxide polyester polyol, full-biodegradable carbon dioxide-based polyurethane and preparation method thereof |
| CN112250845B (en) * | 2020-11-06 | 2022-02-22 | 中国科学院长春应用化学研究所 | Polyester polyol and preparation method thereof |
| CN112538150B (en) * | 2020-11-24 | 2022-02-18 | 中国科学院长春应用化学研究所 | High-resilience polyurethane foam and preparation method thereof |
| CN113493563A (en) * | 2021-07-14 | 2021-10-12 | 扬州工业职业技术学院 | Polyether polyol and preparation method and application thereof |
| CN113773483A (en) * | 2021-09-03 | 2021-12-10 | 山东一诺威新材料有限公司 | Carbon dioxide-based polycarbonate ether polyol for slow-rebound polyurethane foam and preparation method thereof |
| EP4273183A1 (en) * | 2021-09-29 | 2023-11-08 | Lg Chem, Ltd. | Method for manufacturing polyalkylene carbonate resin |
| CN114262430A (en) * | 2021-11-30 | 2022-04-01 | 山东一诺威新材料有限公司 | Carbon dioxide-based polycarbonate ether polyol for solid tires and preparation method thereof |
| CN114957674B (en) * | 2022-06-22 | 2023-06-23 | 烟台大学 | Organosilicon polyol and preparation method thereof |
| CN115851033B (en) * | 2022-12-30 | 2023-12-01 | 杭州普力材料科技有限公司 | Water-based ink connecting agent based on polycarbonate polyether polyol and preparation method thereof, water-based ink and preparation method thereof |
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| CN102432857B (en) * | 2011-08-12 | 2013-01-02 | 中国科学院长春应用化学研究所 | Preparation method of poly(carbonic ester-ether) glycol and preparation method of catalyst thereof |
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